JP4289742B2 - Surface structure of electropolished metal body - Google Patents
Surface structure of electropolished metal body Download PDFInfo
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- JP4289742B2 JP4289742B2 JP29880899A JP29880899A JP4289742B2 JP 4289742 B2 JP4289742 B2 JP 4289742B2 JP 29880899 A JP29880899 A JP 29880899A JP 29880899 A JP29880899 A JP 29880899A JP 4289742 B2 JP4289742 B2 JP 4289742B2
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- metal body
- passive film
- electropolishing
- phosphoric acid
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- 229910052751 metal Inorganic materials 0.000 title claims description 60
- 239000002184 metal Substances 0.000 title claims description 60
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000005498 polishing Methods 0.000 claims description 23
- 150000002894 organic compounds Chemical class 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HKIQCRMZWJSHBZ-UHFFFAOYSA-L dihydroxy(dioxo)chromium phosphoric acid sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O.O[Cr](O)(=O)=O HKIQCRMZWJSHBZ-UHFFFAOYSA-L 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- -1 acetate ester Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Chemical Treatment Of Metals (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、電解研磨を施した金属体、とくに真空雰囲気に曝される状態で使用される金属体の改良された表面構造に関する。
【0002】
【従来の技術】
真空雰囲気を利用した技術は広い産業分野にわたって適用されているが、とくに近年、半導体デバイス製造分野をはじめとして超高真空度が要求される真空装置が実用化されている。かかる真空装置においては、装置を構成する部材として、加工性、軽量、完全非磁性、熱伝導性などが要求される部分にはアルミニウムやアルミニウム合金が主に使用され、反応性、耐腐食性、高強度などが要求される部分にはステンレス鋼が主に使用されている。
【0003】
このような真空装置において、装置を構成する金属部材の表面に微小な掻き傷があると、微細な塵等の付着、あるいはそれによって引き起こされる金属表面の腐食が生じることから、金属部材の表面を電解研磨により微小な傷などのない平滑な面に形成することが行われている。また、真空雰囲気に曝される金属体は、真空雰囲気中において金属体から放出されるガスが少ないことが要求され、様々な表面処理による表面構造の改良が行われている。
【0004】
たとえば、特開平3−180500号公報には、内表面が真空雰囲気に曝されるステンレス鋼製の真空容器内壁を、砥粒による研磨後に電解研磨処理することが記載され、また特開平9−217166号公報には、鉄酸化物よりクロム酸化物が多い層を外側表面に有する不働態膜をステンレス鋼の電解研磨面上に形成することが記載されている。このような電解研磨処理により、表面に微小な傷などのない金属体が得られ、真空雰囲気中における金属体からのガスの放出が低減される。
【0005】
【発明が解決しようとする課題】
上記のような電解研磨において、電解液としては、リン酸、硫酸、クロム酸、硝酸、フッ化物などを単独にまたは組み合わせたものが用いられるが、なかでも硫酸を含む電解液、たとえばリン酸−硫酸−クロム酸系の電解液が多用されている。
【0006】
本発明者は、従来多用されている硫酸を含む電解液に関して、電解研磨後の金属体の表面構造およびこの金属体を真空雰囲気においた場合のガスの放出状況を詳細に調査し、つぎのような問題点があることを見出した。
【0007】
リン酸−硫酸−クロム酸系の電解液を用いて電解研磨した後の金属体を真空度1×10-6Torr以下の高真空雰囲気内に長期間おいたとき、雰囲気内に硫化物系のガスが存在することが検出された。硫化物系のガスは、真空装置を構成する金属部材に装置内腐食を生じせしめ、装置の故障につながる事故の原因となる。このガスは、不働態膜に残存する硫化物が高真空下でガス化して生じたものと推測される。また、金属体が真空雰囲気に曝されると、金属体からはその表面の不動態膜内に残存したガス、水分等が放出され、これらの放出は真空度の上昇を妨げる要因となり得る。よって、真空装置の部品として使用される金属については、真空雰囲気中において金属体表面から放出されるガスの少ないことが要求されている。
【0008】
さらに、電解研磨後の金属体の表面は、同一の成形品でも加工面により切削速度などの加工条件が異なった場合は表面の光沢度が不均一になりやすいという問題がある。また、冷間加工されたステンレス鋼においては、成形加工時の研削加工など金属体が受けた熱履歴により、電解研磨後の表面の光沢度が不均一になりやすい。
【0009】
本発明が解決すべき課題は、真空雰囲気に曝される状態で使用される金属体において、高真空下においても電解研磨された金属体表面から有害なガスを発生せず、かつ、金属体表面からの放出ガスの少ない金属体の表面構造を得ることにある。さらに、加工面により加工条件が異なった金属体においても、所定の範囲に均一な表面光沢度を有する金属体の表面構造を得ることにある。
【0010】
【課題を解決するための手段】
上記課題は、電解研磨された金属体の表面構造を、リン酸と有機化合物とからなる電解研磨液を用いて形成された不働態膜を表面に有する表面構造とすることによって達成される。
【0011】
本発明者らは、真空雰囲気下において電解研磨後の金属体表面から有害なガスが発生する理由とその防止策について種々研究を重ね、つぎのような知見を得た。ここで有害なガスとは、半導体製造装置内での腐食を引き起こすH2 S,SO2 ,SOなどの硫化ガスを指す。
【0012】
真空雰囲気において上記のような硫化ガスの発生を防止するためには、電解研磨後の金属体の不動態膜内に硫黄を含有しないことが望ましい。従来一般に使用されているリン酸−硫酸−クロム酸系の電解液により形成した不動態膜について、X線プローブマイクロアナライザーにより定性分析した結果では硫黄化合物は検出されない。しかし、真空下では硫化物系のガスの放出が検出された。このことから、X線プローブマイクロアナライザーによる定性分析では確認されなかったものの、不動態膜内には微量な硫黄が存在しており、これが硫化物系ガスの放出につながっているものと推測される。
【0013】
また、真空雰囲気におけるガス放出量は、金属体表面の不動態膜の膜厚と関係し、膜厚が厚くなるとガス放出量が増すことが確認された。
【0014】
さらに、同時に電解研磨処理を施したオーステナイト系ステンレス鋼で鏡面光沢を有する部分と有しない部分について表面組織を調査したところ、両者間で表面の結晶組織が異なっていることがわかった。これはオーステナイト組織のものが部品の加工時に熱履歴を受けたか否かで結晶組織が異なっており、熱履歴を受けていない部分はオーステナイト組織のままであったが、熱履歴を受けた部分についてはマルテンサイト組織への変態が確認され、粒界付近にはクロムと炭素化合物の偏析が認められた。そして、このマルテンサイト組織に変態した部分は局部的に他の部分よりも電解研磨が促進され、その結果、この部分は鏡面光沢を呈しない表面状態となっていることが確認された。したがって、表面全体が鏡面光沢を有するようにするためには、金属の過剰な局部的溶解を防止する電解液が必要である。本発明はかかる知見に基づいて創案されたものである。
【0015】
すなわち本発明の特徴は、電解研磨された金属体の表面構造を、リン酸と有機化合物とからなる研磨液を用いて形成された不働態膜を表面に有する表面構造とすることにある。
【0016】
リン酸と有機化合物とからなる研磨液、すなわち硫黄分を含まない研磨液を用いて電解研磨を行うことにより、不働態膜内に硫黄分を有しない金属体表面構造が得られる。これにより、高真空下においても金属体表面から有害な硫化物系ガスが発生しないようにすることができる。
【0017】
また、リン酸以外の副成分として、化学的に金属を溶解する作用が小さい有機化合物を使用することにより、電解研磨時に金属体表面の局部研磨が抑制され、表面粗度の増加が抑制されて、優れた光沢表面が得られる。リン酸と有機化合物の割合は、電解研磨処理する金属体の種類に応じて、リン酸50〜95%、有機化合物5〜50%とする。
【0018】
ここで有機化合物としては、リン酸エステル、炭酸エステル、カルボン酸エステル類の少なくとも一種を含むものを用いる。このような有機化合物としては、たとえば(n−C4 H9 O)3 PO,(CH3 O)3 PO,(C2 H5 O)2 CO,(CH3 CH2 CH2 CH2 O)2 CO,((CH3 )3 CO)2 CO,((CH3 )2 CHCH2 O)2 CO,CH3 COOCH(CH3 )CH2 CH3 ,CH3 COOC(CH3 )3 ,CH3 CH2 COOC2 H5 が挙げられる。これら有機化合物は金属体の種類に応じて電解液の粘度および表面張力を調整するために適宜使用し、各有機化合物の配合は電解研磨処理する金属体の種類に応じて調製する。
【0019】
電解液の組成の具体的な例を挙げると、両性金属であるアルミニウムは酸性溶液と容易に反応するため、電解研磨後の次工程である水洗工程に移る間にアルミニウムとその表面に付着した電解液とが反応する。このような金属体においては、リン酸80%、リン酸エステル((n−C4 H9 O)3 PO)20%の配合で調製することが望ましい。
【0020】
電解研磨によって形成する不働態膜の厚さは、金属体がアルミニウムおよびその合金の場合は700〜2000Å、ステンレス鋼の場合は300Å以上とするのが望ましい。アルミニウムおよびその合金で膜厚が700Å未満、ステンレス鋼で膜厚が300Å未満では耐食性が不十分となる。アルミニウムおよびその合金で膜厚が2000Åを超えると真空下でのガスの放出量が増加するため、真空装置内の真空度の低下につながる。ステンレス鋼においては、異なる電解条件でも不動態膜の厚さは変化しないので、膜厚の上限は限定されない。このような膜厚の不動態膜を形成するには、金属体の形状や素材の種類にもよるが、電圧:6〜12V、液温:30〜70度、また電解時間は不動態膜の厚さに比例する傾向があることから3〜15分として電解研磨すればよい。
【0021】
電解研磨後の金属体表面の粗度はRa で0.20μm以下とするのが望ましい。Ra が0.20μmを超える面粗度では、光沢度が200未満となって表面が白化し、ざらついた外観となる。ここで、光沢度を表す数値は、JIS Z8741(鏡面光沢度測定法)に規定する測定角20度に基づいて測定した数値を用いる。表面粗度をRa 0.20μm以下とするための電解研磨条件は、上記の条件の範囲内で設定する。
【0022】
【実施例】
〔実施例1〕
リン酸80%、酢酸エステル(CH3 COOC(CH3 )3 )20%の電解液を使用して電解研磨によりアルミニウム合金A5052材上に不働態膜を形成し、質量分析装置により真空中での不動態膜内からの放出ガスを調査した結果を表1に示す。比較例としてリン酸−硫酸系の電解液で形成した不動態膜に関する結果を示す。
【0023】
【表1】
【0024】
表1からわかるように、硫黄分を含まない電解液を使用した実施例においては、真空下における不動態膜内からの放出ガスに硫化物系ガスは存在しないことが確認された。アルミニウムおよびその合金については、不動態膜の厚さと真空下でのガス放出速度は比例関係にあり、膜厚が厚くなるほど真空度が劣化する傾向にあることから、実施例における低ガス放出性は、不働態膜の厚さが2000Åを超えると低下する傾向にある。比較例においては、真空下における不動態皮膜内からの放出ガスに硫化物系ガスが含有されており、その分、放出ガス速度も同じ膜厚の実施例と比較して増加する傾向にある。
【0025】
〔実施例2〕
リン酸80%、酢酸エステル(CH3 COOCH(CH3 )CH2 CH3 )20%の電解液を使用してステンレス鋼を電解研磨し、電解研磨後の光沢度について調査した結果を表2に示す。比較例としてリン酸−硫酸系の電解液で電解研磨した後の光沢度を示す。
【0026】
【表2】
【0027】
表2からわかるように、リン酸以外の副成分として、金属溶解作用が小さく低粘性の有機化合物を使用した実施例においては、電解研磨時にステンレス鋼表面の局部研磨が抑制され、表面粗度の増加が抑制されて、従来の電解液を使用した比較例に比べて優れた光沢表面が得られた。なお、SUS440Cについては、素材中の炭素含有量が多いため金属表面の局部研磨が促進され、光沢度が低下したものと考えられる。
【0028】
【発明の効果】
本発明により以下の効果を奏することができる。
【0029】
(1)リン酸と有機化合物とからなる研磨液、すなわち硫黄分を含まない研磨液を用いて電解研磨を行うことにより、不働態膜内に硫黄分を有しない金属体表面構造が得られる。これにより、高真空下においても金属体表面から有害な硫化物系ガスが発生しないようにすることができる。
【0030】
(2)リン酸以外の副成分として、金属溶解作用が小さい有機化合物を使用することにより、電解研磨時に金属体表面の局部研磨が抑制され、表面粗度の増加が抑制されて、優れた光沢表面が得られる。これにより、従来の電解研磨では良好な光沢表面が得られなかったマルテンサイト系ステンレス鋼などでも表面の均一な光沢度を得ることが可能となる。
【0031】
(3)電解研磨によって形成する不働態膜の厚さを、アルミニウムおよびその合金では700〜2000Å、ステンレス合金では300Å以上とすることによって、充分な耐食性を維持したうえで、真空下でのガスの放出を抑制することができる。
【0032】
(4)電解研磨後の表面粗度をRa 0.20μm以下とすることによって、表面の光沢度が200以上となり、良好な光沢表面が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved surface structure of an electropolished metal body, particularly a metal body used in a state exposed to a vacuum atmosphere.
[0002]
[Prior art]
The technology using a vacuum atmosphere has been applied over a wide range of industrial fields, but in recent years, vacuum devices requiring ultra-high vacuum have been put into practical use, particularly in the field of semiconductor device manufacturing. In such a vacuum apparatus, aluminum or an aluminum alloy is mainly used as a component constituting the apparatus for parts that require workability, light weight, complete non-magnetism, thermal conductivity, and the reactivity, corrosion resistance, Stainless steel is mainly used for parts that require high strength.
[0003]
In such a vacuum device, if there are minute scratches on the surface of the metal member that constitutes the device, adhesion of fine dust, etc., or corrosion of the metal surface caused thereby, will occur. Formation on a smooth surface free from minute scratches by electrolytic polishing is performed. Further, a metal body exposed to a vacuum atmosphere is required to have a small amount of gas released from the metal body in the vacuum atmosphere, and surface structures are improved by various surface treatments.
[0004]
For example, Japanese Patent Laid-Open No. 3-180500 describes that an inner wall of a stainless steel vacuum vessel whose inner surface is exposed to a vacuum atmosphere is subjected to electrolytic polishing after polishing with abrasive grains. The publication describes that a passive film having a layer containing more chromium oxide than iron oxide on the outer surface is formed on the electropolished surface of stainless steel. By such electrolytic polishing treatment, a metal body free from minute scratches is obtained on the surface, and the release of gas from the metal body in a vacuum atmosphere is reduced.
[0005]
[Problems to be solved by the invention]
In the above-described electropolishing, as the electrolytic solution, phosphoric acid, sulfuric acid, chromic acid, nitric acid, fluoride, or the like is used alone or in combination. Among them, an electrolytic solution containing sulfuric acid, for example, phosphoric acid- A sulfuric acid-chromic acid electrolyte is frequently used.
[0006]
The present inventor investigated in detail the surface structure of a metal body after electropolishing and the state of gas emission when the metal body was placed in a vacuum atmosphere for an electrolytic solution containing sulfuric acid that has been widely used in the past. I found that there is a problem.
[0007]
When the metal body after being electropolished with an electrolyte solution of phosphoric acid-sulfuric acid-chromic acid is left in a high vacuum atmosphere with a vacuum degree of 1 × 10 −6 Torr or less for a long period of time, sulfide-based metal is not contained in the atmosphere. The presence of gas was detected. Sulfide-based gas causes internal corrosion of the metal members constituting the vacuum apparatus, causing an accident that leads to the breakdown of the apparatus. This gas is presumed to be produced by gasification of the sulfide remaining in the passive film under high vacuum. Further, when the metal body is exposed to a vacuum atmosphere, gas, moisture, and the like remaining in the passive film on the surface are released from the metal body, and these releases can be a factor that hinders the increase in the degree of vacuum. Therefore, a metal used as a part of a vacuum apparatus is required to have a small amount of gas released from the surface of the metal body in a vacuum atmosphere.
[0008]
Furthermore, the surface of the metal body after electropolishing has a problem that the glossiness of the surface tends to be nonuniform even when the processing conditions such as the cutting speed differ depending on the processing surface even in the same molded product. In addition, in cold-worked stainless steel, the glossiness of the surface after electropolishing tends to be non-uniform due to the thermal history received by the metal body such as grinding during molding.
[0009]
The problem to be solved by the present invention is that, in a metal body used in a state exposed to a vacuum atmosphere, no harmful gas is generated from the surface of the electropolished metal body even under high vacuum, and the metal body surface The object is to obtain a surface structure of a metal body that emits less gas from the metal. Furthermore, it is to obtain a surface structure of a metal body having a uniform surface glossiness within a predetermined range even in a metal body having different processing conditions depending on the processed surface.
[0010]
[Means for Solving the Problems]
The above-mentioned subject is achieved by making the surface structure of the electropolished metal body into a surface structure having a passive film formed on the surface using an electropolishing liquid composed of phosphoric acid and an organic compound.
[0011]
The inventors of the present invention have made various studies on the reason why harmful gas is generated from the surface of a metal body after electrolytic polishing in a vacuum atmosphere and the preventive measures thereof, and have obtained the following knowledge. Here, the harmful gas refers to a sulfur gas such as H 2 S, SO 2 , and SO that causes corrosion in the semiconductor manufacturing apparatus.
[0012]
In order to prevent the generation of sulfide gas as described above in a vacuum atmosphere, it is desirable not to contain sulfur in the passive film of the metal body after electropolishing. Sulfur compounds are not detected as a result of qualitative analysis using an X-ray probe microanalyzer for a passive film formed with a phosphoric acid-sulfuric acid-chromic acid electrolyte that is generally used. However, the release of sulfide gas was detected under vacuum. From this, although it was not confirmed by the qualitative analysis by the X-ray probe microanalyzer, it is presumed that a trace amount of sulfur exists in the passive film, which leads to the release of sulfide-based gas. .
[0013]
In addition, the gas release amount in the vacuum atmosphere is related to the thickness of the passive film on the surface of the metal body, and it was confirmed that the gas release amount increases as the film thickness increases.
[0014]
Further, when the surface structure of the austenitic stainless steel subjected to the electrolytic polishing treatment at the same time and the part having no specular gloss were investigated, it was found that the surface crystal structures were different between the two. This is because the crystal structure differs depending on whether the austenitic structure was subjected to thermal history during processing of the part, and the part that did not receive the thermal history remained the austenitic structure, but the part that received the thermal history Was confirmed to be transformed into a martensite structure, and segregation of chromium and carbon compounds was observed near the grain boundary. And the part transformed into this martensite structure was locally promoted by electropolishing than other parts, and as a result, it was confirmed that this part was in a surface state that did not exhibit specular gloss. Therefore, in order for the entire surface to have a specular gloss, an electrolyte that prevents excessive local dissolution of the metal is required. The present invention has been created based on such knowledge.
[0015]
That is, the present invention is characterized in that the surface structure of the electropolished metal body is a surface structure having a passive film formed on the surface using a polishing liquid composed of phosphoric acid and an organic compound.
[0016]
By performing electrolytic polishing using a polishing liquid composed of phosphoric acid and an organic compound, that is, a polishing liquid that does not contain sulfur, a metal body surface structure that does not have sulfur in the passive film is obtained. Thereby, it is possible to prevent generation of harmful sulfide-based gas from the surface of the metal body even under high vacuum.
[0017]
In addition, by using an organic compound that has a small effect of chemically dissolving a metal as a secondary component other than phosphoric acid, local polishing of the surface of the metal body is suppressed during electrolytic polishing, and an increase in surface roughness is suppressed. , An excellent glossy surface is obtained. The ratio of phosphoric acid and organic compound is set to 50 to 95% phosphoric acid and 5 to 50% organic compound depending on the type of metal body to be electropolished.
[0018]
Here, as the organic compound, an organic compound containing at least one of phosphoric acid ester, carbonic acid ester and carboxylic acid ester is used. As such an organic compound, for example, (n-C 4 H 9 O ) 3 PO, (CH 3 O) 3 PO, (C 2 H 5 O) 2 CO, (CH 3 CH 2 CH 2 CH 2 O) 2 CO, ((CH 3 ) 3 CO) 2 CO, ((CH 3 ) 2 CHCH 2 O) 2 CO, CH 3 COOCH (CH 3 ) CH 2 CH 3 , CH 3 COOC (CH 3 ) 3 , CH 3 CH 2 COOC 2 H 5 is mentioned. These organic compounds are appropriately used for adjusting the viscosity and surface tension of the electrolytic solution according to the type of the metal body, and the blending of each organic compound is prepared according to the type of the metal body to be subjected to the electropolishing treatment.
[0019]
To give a specific example of the composition of the electrolyte, aluminum, which is an amphoteric metal, easily reacts with an acidic solution, so the aluminum and the electrolyte attached to its surface during the next water washing step after electropolishing. The liquid reacts. In such a metal member, 80% phosphoric acid, phosphoric acid esters ((n-C 4 H 9 O) 3 PO) it is desirable to prepare a 20% formulation.
[0020]
The thickness of the passive film formed by electropolishing is desirably 700 to 2000 mm when the metal body is aluminum and its alloy, and 300 mm or more when the metal body is stainless steel. If the film thickness is less than 700 mm with aluminum or an alloy thereof and the film thickness is less than 300 mm with stainless steel, the corrosion resistance will be insufficient. If the film thickness of aluminum and its alloy exceeds 2000 mm, the amount of gas released under vacuum increases, leading to a decrease in the degree of vacuum in the vacuum apparatus. In stainless steel, since the thickness of the passive film does not change even under different electrolysis conditions, the upper limit of the film thickness is not limited. In order to form a passive film having such a film thickness, although it depends on the shape of the metal body and the type of material, the voltage is 6 to 12 V, the liquid temperature is 30 to 70 degrees, and the electrolysis time is the same as that of the passive film. Since there is a tendency to be proportional to the thickness, the electropolishing may be performed in 3 to 15 minutes.
[0021]
The roughness of the surface of the metal body after electropolishing is preferably 0.20 μm or less in terms of Ra. When the surface roughness is greater than 0.20 μm, the gloss is less than 200, the surface is whitened, and a rough appearance is obtained. Here, as the numerical value representing the glossiness, a numerical value measured based on a measurement angle of 20 degrees defined in JIS Z8741 (mirror glossiness measurement method) is used. The electrolytic polishing conditions for setting the surface roughness to Ra 0.20 μm or less are set within the range of the above conditions.
[0022]
【Example】
[Example 1]
A passive film was formed on the aluminum alloy A5052 material by electrolytic polishing using an electrolytic solution of 80% phosphoric acid and 20% acetic acid ester (CH 3 COOC (CH 3 ) 3 ). Table 1 shows the results of investigating the gas released from the passive film. The result regarding the passive film formed with the electrolyte solution of a phosphoric acid-sulfuric acid system as a comparative example is shown.
[0023]
[Table 1]
[0024]
As can be seen from Table 1, in the examples using the electrolytic solution containing no sulfur content, it was confirmed that there was no sulfide-based gas in the gas released from the inside of the passive film under vacuum. For aluminum and its alloys, the thickness of the passive film and the gas release rate under vacuum are in a proportional relationship, and as the film thickness increases, the degree of vacuum tends to deteriorate. When the thickness of the passive film exceeds 2000 mm, it tends to decrease. In the comparative example, a sulfide-based gas is contained in the gas released from the inside of the passive film under vacuum, and accordingly, the gas release rate tends to increase as compared with the example having the same film thickness.
[0025]
[Example 2]
Table 2 shows the results of investigating the glossiness after electrolytic polishing of stainless steel using electrolytic solution of 80% phosphoric acid and 20% acetate ester (CH 3 COOCH (CH 3 ) CH 2 CH 3 ). Show. As a comparative example, the glossiness after electropolishing with a phosphoric acid-sulfuric acid electrolyte is shown.
[0026]
[Table 2]
[0027]
As can be seen from Table 2, in the example using a low-viscosity organic compound having a small metal dissolving action as a secondary component other than phosphoric acid, local polishing of the stainless steel surface was suppressed during electropolishing, and the surface roughness was reduced. The increase was suppressed, and an excellent glossy surface was obtained as compared with the comparative example using the conventional electrolytic solution. In addition, about SUS440C, since there is much carbon content in a raw material, the local grinding | polishing of a metal surface is accelerated | stimulated and it is thought that the glossiness fell.
[0028]
【The invention's effect】
The following effects can be achieved by the present invention.
[0029]
(1) By performing electrolytic polishing using a polishing liquid composed of phosphoric acid and an organic compound, that is, a polishing liquid that does not contain sulfur, a metal body surface structure that does not have sulfur in the passive film is obtained. Thereby, it is possible to prevent generation of harmful sulfide-based gas from the surface of the metal body even under high vacuum.
[0030]
(2) By using an organic compound having a small metal dissolving action as an auxiliary component other than phosphoric acid, local polishing of the surface of the metal body is suppressed during electrolytic polishing, and an increase in surface roughness is suppressed, resulting in excellent gloss. A surface is obtained. This makes it possible to obtain a uniform glossiness on the surface of martensitic stainless steel, etc., for which a good glossy surface could not be obtained by conventional electropolishing.
[0031]
(3) The thickness of the passive film formed by electropolishing is 700 to 2000 mm for aluminum and its alloys, and 300 mm or more for stainless alloys, so that sufficient corrosion resistance is maintained and the gas in a vacuum is maintained. Release can be suppressed.
[0032]
(4) By making the surface roughness after electropolishing Ra 0.20 μm or less, the glossiness of the surface becomes 200 or more, and a good glossy surface is obtained.
Claims (4)
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